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Патент USA US2411142

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Patented Nov. 19, 1946
/ 2,411,142
,. UNITED" STATES PATENT‘ , QFFECE
2,,d115142
smrns'rro FUSIBLE AMINE nnsms AND
/
'rnE METHOD or oarsmmn run salon
Charles‘ D. Kelso, Crete, 111.‘, and Chester E.
Adams, Highland, ind, assignors to Stanrd _‘
Oil Company, Chicago, Ell" a corporation or
,
j
Indiana,
0
‘No Drab s t ‘r:
Application April 30, 1948,
‘ .Serlaji No. scares
'
12 (ilaims.
(Cl. zoo-+2)
This invention relates to improvements in fusi~
ble synthetic resins and more particularly re
within the range of about 140 to about 350° F.
and under a pressure sumcient to maintain the,
reactants in a liquid phase. The reaction time
latejs to fusible synthetic amine resins and to
their preparation.
Certain types of dii?cultly fusible or substan
tially infusible synthetic resins are obtained byv
obviously varies with the reaction temperature
and may be a matter of minutes to a matter of
days. When'the reaction is conducted within the
preierredrolnge: namely, from about 140° F. to
reacting aromatic compounds‘ having at . least
two halcalkyl groups substituted in the aromatic
nucleus with aqueous ammonia at temperatures
about 350° F, the reaction time varies from about
one-half hour to about thirty hours.
The concentration of the aqueous ammonia
solution can be varied depending upon the poly
below about 480° 3". preferably at a temperature ,
of from about 140° F. to about 250° F. and under
su?icient pressure to maintain the reactants in
the liquid phase.
“
(haloallryl) aromatic compounds used and upon ~
-
.the reaction conditions. However, in any case‘,
the aqueous ammonia solution should be sum
The aromatic component of the reaction is
mono-nucleated or poly-nucleated aromatic com
pound having at least two active haloalkyl groups ~
ciently concentrated to avoid hydrolysis or the,
di(halcalkyl) aromatic compound. Since su?l
preferably chloroalkyl and bromoalkyl groups, -
cient basic material functioning as an acid ao
substituted in the aromatic nucleus. The halo
' ceptor should be used in carrying out the reac
alkyl substituents are prei'erably halomethyl
tion, the ammonia may constitute the sole basic '
‘groups and more preferably are halomethyl' 20 material employed acting both as a reactant and
groups in non-adjacent positions in the ring. In
an acid acceptor or other basic compounds
addition to the haloalkyl substituents the nucleus
such as, for example, basic metallic hydroxides,
‘ may contain other hydrocarbon substituent
and oxides, and basic organic compounds such
groups such as alkyl, cyclo alkyl- and other aryl , as dimethyl‘anilinei pyridine or any other ‘or-,
groups.
'
The term “active haloalkyl groups" as em
‘ played in the above'de?nition means such halo
alkyl groups which are capable of precipitating
.a silver halide from a silver nitrate solution in
the cold;
Di(chloromethy1) naphthalenes
fDi(chloromethyl) benzenes \
Di(brcmomethy1) naphthalenes
Di(bromomethyl) benzenes
Di(chloromethyl) toluenes
.
Di(bromomethy1) toluenes
Di(chloromethyl) mesitylene
a,a'-Dichlorodurenes
a,a'-Dichlorolsodurenes
a,a'-Dichloroprehnitene
Di(chloromethyl) methyl naphthalene
Di(chloromethyl) diethylbenzene
Di(bromomethyl) methyl naphthalene
Trl(ch1oromethyl) naphthalene _
Dl(chloroethyl) naphthalene ‘
and others.
'
ployed in conjunction therewith. In the absence
of another basic material as an acid acceptor,
the amount or ammonia used should be in excess
of 8 mols or
outs for each 6 mole of halogen
30 in the aromatic compound employed.
.
Representative of the class 01' aromatic com
pounds which is employed in the preparation of
such resins are the following:
V
26 ganic base tree oi amino hydrogen may be em- ‘
~
'
The polyamine synthetic resins are obtained
by reacting suitable poly(haloalkyl) aromatic
compounds of the above type with aqueous am
monia at room temperature or higher but below
when
other basic materials are employed as the acid
acceptor, the, amount of aqueous ammonia em
ployed is correspondingly reduced. . Thus, when
none of the aqueous aonia is utilized as the
35 acid acceptor, 2 mole of ammonia is'used for each
datoms or halogen in the aromatic compound. 1
While it is preferable to employ ‘aqueous am
monia tor the synthesis or these polyamine res
ins, aqueous solutions of water soluble primary
40 amines, preferably alkyl mono- or ‘polyamines .
can be used in ‘combination with aqueous am-_
monla.
~
In conducting the reaction suitable inert or
non-reactive diluents can be employed such as,
for example, other, hexane, dioxane, benzene.
toluene and the like.
‘
-
The rollowing'examples vare illustrative of the
methods or obtaining infus'ible’ polyamlne resins
of the herelndescribed types.
50
Emple I
Twenty grams oi‘ 2,4‘é-dichlorodurene were re
acted at 170° F. with 200 cc. 0! a concentrated
aqueous ammonia solution. Although the reac
about 480° F. and preferably at a temperature’ 55 tion moss solidi?ed in one-halt hour, the reaction
,
2,411,142
3
a
4
of the resin, for example at a temperature be
was continued for two hours. After boiling with
acetone and water a product yield of 2.5 grams
was obtained. The washed material was treated‘
tween about 250‘? F. and about 475° F. The‘ length
of time for the treatment will vary, since it is
‘dependent upon the temperature and the amount
of softening agent employed. Suitable com
with a hot 5%. solution of sodium hydroxide for -
two hours and an infusible, but moldable resin
pounds are the mono-nucleated or poly-nucleated
ous material obtained.
aromatic compounds having one or more halo-_
Example II n
’
Twenty grams of 2,4-dichlorodurene were re
1 acted with 200 cc. of a concentrated aqueous am
, monia solution for four hours at 120° F. An ad
alkyl groups substituted in the aromatic nucleus
such as, for example, the following representative
lo speci?c compounds:
Di(chloromethyl) naphthalene
ditional 100cc. of aqueous NH: were added and
Di(chloromethyl) benzene
the reaction continued for four more hours. The‘ - Di(br‘omorhethyl) naphthalene
reaction mass was ?ltered and extracted twice ;, Di(bromomethyl) benzene
with boiling acetone. A yield of 6.5 grams of a -
.Di(chloromethyl) toluene
moldable resinous material was obtained.
Example III
Di(bromomethyl) toluene
Di(chloromethyl) mesitylene
a,a'v-Dichloroprehnitene
Five grams of di(chloromethyl) naphthalene
a,a'-Dichloroisodurene
were reacted with 200 cc. of a 28% aqueous solu 20 a,a’-Dichlorodurene
Benzyl chloride
tion of NH3 in a shaker bomb at 250° F. ‘to 260° F.
a-Chloroxylenes
for about twenty-one'hours. ‘At the end of this I
a-Chloromesityiene
time the temperature increased to 335° F., heat
ms was stopped and the reaction products shaken
a-Cholorotrimethylbenzenes
for another hour, making- a total reaction-time 25 (Chioromethyl) naphthalene
of twenty-two hours. i
.
.
a-Choloroprehnitene
_
Di(chloromethyl) methyl naphthalene
The .bomb was opened and the contents thereof
filtered. The solid material was washed with
water and dried~atr220° F., and a yield of 3.4
Di(chloromethyl) vdi ethyl benzene
.
Di(bromomethyl) methyl naphthalene ~
grams of solid material obtained. The resinous 30
Di(chloroethyl) naphthalene.
material was molded with a platen .temperature
of 450° F. and 8000 pounds per'square inch. A
molding with a very hard surface was obtained.
and others. Other organic halides which are
suitable are the hydrocarbon halidessnch as tri
..
'
Example IV
35
One gram of 1,5-di(chloromethyl)' naphthalene
and 5 cc. of a 28% aqueous ammonia solution
methylene dibromide, ethylene dichloride, amyl
chloride, amyl bromide, hexyi chloride, dichlcropentane, dichlorobutene, dibrornocyclohexane and‘
the like. Organic acid halides such as,_for ex
. ample, acetyl chloride, acetyl bromide, benzoyl
, were heated in an oven in a sealed tube at 172°. F.
chloride, succinyl chloride, benzene sulfone chlo
for forty hours. The contents of the tube were 40 ride and the like are‘; suitable softening‘ agents.
then removed to a ?ask and re?uxed with 200 cc.
of water for two hours. The material was then
Mixtures of two or more of any of the foregoing
types of organic halides can be employed. '
' ?ltered and dried and a solid material weighing,
In order to clearly set forth the present inven
,85 gram was'obtained. The material was in
tion, the same will be described in connection
soluble in boiling hexane and boiling methyl 45 with the modi?cation of the synthetic amine
naphthalene. The resinous material was molded
resins of the hereinbefore-described type in which
at a. platen temperature of 425° F. and 8000
aromatic compounds having at least two active
pounds per square inch. The molding obtained ‘ haloalkyl groups substituted in the aromatic nu
was hard with a high polish.
‘
cleus are reacted with aqueous ammonia solu-v
The synthetic resins ofv the foregoing type, as sotions. his to be understood, however, that the
well as other amine-type resins, while suitable
present invention is not limited to the modiflca- for certain purposes,.are in some respects unde
tion of resins so prepared but is broadly directed
sirable in that they are substantially infusible at
to the modi?cation of any substantially infusible
molding temperatures; that is, the softening point
syntheticamine resin such as, for example, the
of such resins is higher than the usual molding
synthetic resin v.of the
type described in. U. ‘S.
'55
.
temperatures and‘ hence the material does not
Patent 2,268,620 issued to G. W. Rigby January
fuse to give a desirable transparent or trans
6, 1942. Accordingly the present invention isv
lucent resinous material.
a '
It is the ‘object of the present invention to‘
provide- an improved method of lowering the
softening point of .substantially infusible syn
thetic resins of the amine type. Another object
of the present invention is to provide a method
of modifying synthetic amine resins for the pur
pose of lowering the molding temperature thereof.
Still another object of the invention is to provide 65
fusible synthetic amine resins.
‘
We have discovered‘that the foregoing objects
illustrated by the following examples:
Example V
Twenty grams of 2,4-dichlorodurene were re
acted with 200 cc. of a concentrated aqueous am
monia solution for four hours at 120° F. An ad
ditional 100 cc. of aqueous ammonia were then
added and the reaction continued for four more
hours and the reaction mass ?ltered and twice .
extractedwith boiling acetone. A resinous ma
terial was obtained which was incompletely fused
when molded at a. temperature of 400° F. under a
halogenated organic compound, such as 'an or
ganic halide or an organic acid halide, which is ‘:0 pressure of 16,000 pounds per square inch.
One gram of resinous material was then mixed
capable of adding to a tertiary amino nitrogen
atom to form a quaternary compound. The _ with .15 gram of 2,4-dichlorodurene and the mix
ture molded at 400° F. under a pressure of 16,000
chlorinated compounds are preferably employed.
pounds per square inch. Av completely fused
The treatment is carried out at an elevated tem
can be attained by-treating suchresins with av
perature, preferably at the molding temperature
76 molding was obtained.
-
_
-
2,4111,143
will determine the completeness oi.’ the reaction
between the aqueous ammonia and the_di(halo
alkyl) aromatic but also the temperature, strength‘
Example Vi’
One hundred forty grams of ui-dichlorodurene
were reacted with 1000 cc. of a 15% aqueous solu
tion of ammonia at 140° F. for eighteen hours.
The solid reaction material was washed with cold
of aqueous ammonia and the available amount ‘
of ammonia for the reaction.
In softening infusible amine resins with halo-=
genated organic compound it is essential to avoid
the use of an excessive amount of the latter since
water and dried with alcohol and ether. The
washed material was then twice extracted with
hot benzene, ?ltered and dried.
The resinous
the use of too great a quantity of the softening '
material obtained was infusible when molded at
400° F. and under a‘ pressure of 10,000 pounds
per square inch.
material will lower the softening point of the
resin to a degree which vwill render the resin
'
brittle.
’
a
‘
A portion of the above resinous material was
Since many embodiments of this invention may
re?uxed with a 5% solution of sodium hydroxide
be made without departing from the spirit and
for several hours. One hundred parts of this 15
scope thereof, it is to be understood that the in
caustic treated resinous material was theniniaed
. vention is not limited to the specific examples and
with ?fteen parts of 2,d=dichlcrodurene and the
embodiments described herein, except as de?ned
‘mixture molded at @150“ 2?‘. under a pressure of
in'the. appended claims.
’
_
10,000 pounds per suuare inch. a substantially
completely fused molding was obtained.
' Eleven grit-mos
thalenc and
reacted for st
hours at ldtl“
refluxed for two
of hill diichloromethyl) naphm
cc.
lé% suueous hil-lh were
or hours at ltd“ if“. and for sin
‘"iThe solid product was ?ltered,
hours in .5350 cc. oi? 1% aqueous
EOE, filtered, washed with
and dried.
A portion. of the resin was molded at i00° l5‘.
We claim;
20
-'
,
'
‘
1. As a new composition of matter a fusible
synthetic amine resin obtained by the process
comprising reacting in the liquid phase a di=
(chloromethyl) naphthalene with aqueous and»
mania sumciently concentrated to avoid hydrolu
ysis of the cli(chloromethyl) naphthalene, and at
least one~third moi of ammonia being used for
each chlorine atom in the di (chloromethyll naphn
thalene and heating the resultant amine resin
at a temperature of from about 250° F. to about‘
under 16,000 pounds per square inch-for ?fteen 30 475°
F. with a hydrocarbon halide containing not
more than two halogen atoms in the molecule,
and wherein the halogen atoms are attached to
seven parts ‘of benzoyl chloride in hexane solu»
aliphatic
carbon atoms. said hydrocarbon halide
tion and the resulting mixture evaporated to re
being capable of adding-to a tertiary amino ni
move hexane. 0n molding the mixture at 400° 35 trogen
atom.
F. under ‘16,000 pounds per square inch for fifteen
2. As a new composition of matter a fusible
minutes a strong, fused molding resulted.
synthetic amine resin obtained by the process
In the foregoing examples we have demon
comprising reacting in the liquid phase a di
strated the softening e?ect of certain halogen
ates organic compounds upon dimcultly fusible 40 (chlcromethyl) xylene with aqueous ammonia
sufficiently concentrated to avoid hydrolysis of‘
synthetic amine-type resins. Similar results are
the di(chloromethyl) xylene, and at least one
obtainable by carrying out the reactions in such
third mcl of ammonia being used for each chlo
a manner that not all of the di(haloalkyl)‘ aro
rine atom. of the di(chloromethyl) xylene and
matic compound reacts with the ammonia, as
heating the resultant amine resin at a tempera
illustrated by the following example:
45
ture oi'from about 250° F. to about 475° F. with
\
'
Emmple WU
.
a hydrocarbon halide containing not more than
7 minutes, the molding obtained being unfuse'd.
To one hundred parts of the resin was added
One hundred forty grams of 2,¢i-dichlorodurene
two halogen atoms in the molecule, and wherein
per square inch, yielding a fused, transparent
molding. The second portion was extracted with
boiling benzene, approximately 10 % of the weight
trated aqueous ammonia with an aromatic ‘hydroe
carbon having at least two active haloallryl groups
the halogen atoms are attached to aliphatic car
and 1000 cc. of 14% aqueous ammonia. were ,
bon atoms, said hydrocarbon halide being ca»
heated at ld0° F. with stirring for 24 hours. The 50 pable of adding to a tertiary amino nitrogen
reaction temperature was raised tc"1'75° F. and
atom.
held for seven hours under atmospheric pres~
3. The method of'lowenng the softening point
sure. The product was filtered, washed with we»
of cli?cultly“ fusible synthetic amine resins ob
ter'and divided into two parts. One portion was
tained by reacting in the liquid phase concen
dried and molded at 450° F. and 16,000 pounds
capable of precipitating a silver halide from a sil= '
vernitrate solution-in the cold substituted in the
of the resin being removed. A substantial por
aromatic nucleus. said aqueous ammonia being
. tion of this extract was identi?ed as unchanged 60
sufficiently concentrated to avoid hydrolysis of the
2,4-dichlorodurene. The benzene insoluble resin
aromatic hydrocarbon and. at least two mole of
when molded at 4509 F. and 16,000 pounds per
ammonia being used for each six atoms of halo
square inch gave a chalky uni'used molding.
gen in the aromatic hydrocarbons, comprising
In Example VIE we impart fusible properties
heating said resin at a temperature of from about
‘ by leaving in the product unreacted di(haloal 65 260° F. to about 475° F. with a halogenated or
kyl) aromatic, the amount being left in the resin
ganic compound capable of adding to a tertiary
depending upon the desired softening tempera
amino nitrogen atom selected from the group con
ture. [For example, at different times as the re
sisting of a hydrocarbon halide containing not
action progresses samples of the reacted mate
‘ more than two halogen atoms in the molecule,
70
rial are examined to determine the amount of
and wherein the halogen atoms are attached to
di(haloalkyl) aromatic and the fusibility of the ~ aliphatic carbon atoms and an organic acid hal- l
product, and the reaction of the main body of
ide containing not more than two acyl halide
the material is allowed to proceed until the de
groups attached to a. hydrocarbon residue.
sired residue of unreacted di(haloalkyl) aromatic
The method described in claim 3 in which
is obtained. Obviously not only the time factor 75 the4. aromatic
hydrocarbon is a poly<haloalkyD
2,411,143
-
.
7
.,
.
poly-nuclear aromatic hydrocarbon having at
least two active haloalkyl groups, capable of pre
cipitating a silver halide from a silver nitrate
solution in the cold, substituted in the aromatic ~
nucleus.
(chloroalkyl) aromatic hydrocarbon.
-,
11. vAs a new composition or matter the syn
thetic fusible amine resin obtained by the process
ofv claim 3.
solution in the cold, substituted in the aromatic
v
,
'
,
‘12. The method of lowering the softening point
of di?icultly fusible synthetic amine resins ob
cipitating a silver halide from a silver nitrate
,
.
and the halogenated organic compound is a di
1
5. The method described in claim 3 in which
the aromatic hydrocarbon ,is a poly(haloalkyl)
mono-‘nuclear aromatic hydrocarbon having at ;
least two active haloalkyl groups, capable or pre
nucleus.
8
the aromatic hydrocarbon is a di(chloroalkyl)
aromatic hydrocarbon, said di(chloroalkyl)
groups being capable of precipitating a silver
halide from a silver nitrate solution in the cold
' tained by reacting in the liquid phase concen-v
trated aqueous ammonia with an aromatic hy
i
6. The method described in claim 3 in which
drocarbon having at least two active haloalkyl
ylated) aromatic hydrocarbon having at least 15 ‘groups capable of precipitating the silver halide
from a silver nitrate solution in the cold substi
two chloromethyl groups capable of precipitating
tuted in the aromatic nucleus, said aqueous am
a silver halide from a silver nitrate solution in
monia being su?iclently concentrated to, avoid hy
the cold, substituted in the aromatic nucleus.
the aromatic hydrocarbon is ‘a poly(chlorometh
. drolysis or the aromatic hydrocarbon and at least‘
'7. The method described in claim 3 in which
two mols of ammonia being 'used for each six
20
the aromatic hydrocarbon is a di(chloromethyl)
atoms of halogen in the aromatic hydrocarbon,
naphthalene.
'
‘
comprising mixing said resin with a hydrocarbon
a. The method described in claim a in which,
halide containing not more than two halogen
the aromatic hydrocarbon is‘ a di(chloromethyl)
atoms .inthe molecule, and wherein the halogen j
xylene.
‘
'
’_
atoms are attached‘ to aliphatic carbon atoms.‘
9. The method described in claim 3 in which 25 said
hydrocarbon halide being capable of adding
the aromatic hydrocarbon is a di(chloroalkyl)
aromatic hydrocarbon, said di (chloroalkyl)
groups being capable of precipitating a silver
I
halide from a silver nitrate solution in the cold
and the halogenated organic compound is a 80
mono(chloroalkyl) aromatic hydrocarbon.
10. The method described in claim 3 in which
to a tertiary amino nitrogen atom, and heating
the mixture to a temperature of from about 250°
F. t6 about 475° F.
'
'
CHARLES D. KELSO.
.1 ’
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